Reaction products of certain cationic compounds with anionic compounds,compositions containing same and methods for preparing same

ABSTRACT

REACTION PRODUCTS OF COMPOUNDS OF:   R-(X-R3)N-N(-Y)(-R1-OH)(-R2-OH)-C2H4-OH   AND COMPOUNDS OF: FORMULA II   E-AM-Z-M

United States Patent 015cc 3,661,945 Patented May 9, 1972 3,661,945REACTION PRODUCTS OF CERTAIN CATIONIC COMPOUNDS WITH ANIONIC COMPOUNDS,COMPOSITIONS CONTAINING SAME AND METHODS FOR PREPARING SAME Hans S.Mannheimer, 23 Hains Cove Drive,

Toms River, NJ. 08753 No Drawing. Filed Mar. 27, 1970, Ser. No. 23,453Int. Cl. C07c 143/90 U.S. Cl. 260-401 14 Claims ABSTRACT OF THEDISCLOSURE Reaction products of compounds of:

Formula I R-(X-RzM-N-Rz-OH and compounds of:

Formula II BACKGROUND OF THE INVENTION Organic anionic surface activeagents and organic cationic surface active agents have been known to theart. Based upon the experiences of those skilled in the art in thereaction of cationic and anionic organic surface active agents whichhave been tried, and thereby resulting in the production ofwater-insoluble precipitates, a general rule has evolved thatwater-insoluble precipitates would always be produced in such reactions.

CROSS REFERENCE TO RELATED APPLICATION U.S. Patent application of HansS. Mannheimer, the applicant herein, Ser. No. 883,268 filed Dec. 8,1969.

SUMMARY OF THE INVENTION It was unexpected and surprising to discoverthat water soluble reaction products and compositions of mattercontaining same were produced when a particular group of cationicorganic surface active agents, namely the quaternary ammonium salts ofthe Formula I before set forth were reacted in an aqueous system withanionic organic detergent surface active agents of the Formula II beforeset forth. Among the methods which are employed to carry out thereaction is to provide an aqueous solution of one or a combination oftwo or more compounds of Formula I and then combine therewith one or acombination of two or more compounds of Formula II which may or may notbe in aqueous solution, or one or a combination of two or more of thedifiicultly soluble compounds of Formula I may be added to water andcombined with one or a combination of two or more compounds of FormulaII which may or may not be in aqueous solution and heated to andmaintained at elevated temperature up to about 100 C. to cause solutionof the compounds of Formula I for reaction with compounds of Formula II.Also if desired, even when compounds of Formula I are first in solutionbefore the addition of compounds of Formulas II, such mixtures may beheated to and maintained at elevated temperatures up to 100 C.

In general the reaction products and compositions of this invention arepreferably produced by providing an aqueous solution of one or acombination of two or more compounds of Formula I which is combined withan aqueous solution of one or a combination of two or more compounds ofFormula II. The ratio by weight of the compounds of Formula I to thecompounds of Formula II so combined is in the range of about 1-2-0 toabout 1-1 and preferably about l-l5 to l-4, and the ratio by weight ofwater to the combined weights of the compounds of Formulas I and II isin the range of about 99.8-.2 to about 30-70.

The novel reaction products and compositions of this invention findapplication as hair conditioners in shampoos and laundry detergents,generally those of the high concentrations are more suitable as hairconditioners and those of the lower concentrations as laundrydetergents. They are highly efficient hair and skin conditioners,without reducing foaming as do the more conventional conditioners whichfor the most part are super-fatting agents. They also find applicationas components in conventional shampoos, facial cleansers and the like.It is understood, of course, that those of high concentration may bediluted with water to provide the low concentration solutions forlaundry detergent uses. Particularly suitable for this purpose are suchsolutions wherein the ratio of the combined weights of compounds ofFormulas I and II employed to water is in the range of about 0.2-99.8 toabout 1-99.

In all of the formulas and groups hereinbefore and hereinafter setforth, unless otherwise defined;

R is a hydrocarbon radical of 8-24 carbon atoms and is alkyl orolefinic; (By the term olefinic employed in the present description andclaims, I mean an open chain, straight or branch, hydrocarbon radicalhaving l-4 ethylenic linkages therein).

Each R R and R is an alkylene group of atoms:

X is 000, 0-N

R is hydrogen or alkyl of 1-4 carbon atoms;

E is a hydrocarbon radical of 6-18 carbon atoms and is alkyl or olefinicor alkyl-aryl, with the aryl portion being mononuclear (-C H and thealkyl portion being 6-12 carbon atoms;

Z is S0 0-80 or COO when n is zero and Z is S0 E is alkyl or alkyl-aryl;when n is zero and Z is 0-80 E is alkyl or olefinic; when m is 1 and Zis COO, E is alkyl, olefinic or alkylaryl 2-4 carbon and A is(HJ1\I/I-R5 0 R5 when m is 1 and Z is O-SO E is alkyl, olefinic oralkylaryl and A is (O--R or o-M-R 1's and when m is 1 and Z is S0 E isalkyl, olefinic, or alkylaryl, A is C-M-R; l l.

R is hydrogen or methyl; when R is methyl, R is CH when R is hydrogen, Ris 2- 2 or (3H R is hydrogen, an alkyl radical of 1-4 carbon atoms or analkylol radical of 2-4 carbon atoms;

M is hydrogen, sodium or potassium or obvious equivalent such ammoniumor other monovalent cation;

Y is bromine or chlorine;

n is zero or 1;

m is zero or 1;

x is l-12.

The compounds of Formula I and aqueous solutions thereof may be producedby following the procedures described in my copending US. Patentapplication, Ser. No. 883,268, filed Dec. 8, 1969. That entireapplication is hereby incorporated herein and by this reference shallhave the same force and effect as if it was in its entirety recitedherein.

As set forth in my copending application, compounds of the formula z-OHare reacted with ethylene halohydrin (YC H OH) in an amount of watermeasuring at least 100% of the combined weights of said reactants toproduce aqueous solutions of the resultant quaternary ammonium salts ofFormula I.

The general method for producing said solutions of compounds of FormulaI is to charge the desired amount of water into a reaction vesselequipped with a stirrer and reflux condenser. About 1 mole of a reactantof the formula and about 1.1 to 1.5 moles of the halohydrin reactant isthen added to the water in amount at least equal to and generally aboutl-20 times the combined weights of said reactants. The mass is heated toreflux (boiling under a reflux condenser) at about 105 -110 C. whilebeing constantly stirred over a period of about 8l6 hours or until thereis no change in the pH after further refluxing. At the end of thatperiod the reaction is substantially completed and there is obtained aclear about 505% solution of the resultant quaternary ammonium saltmeasuring at least 90 and generally about 95% of theoretical.

The following are illustrative of examples specific compounds of FormulaI which may be employed in the practice of this invention and methodsfor preparing aqueous solutions thereof.

EXAMPLE 1 1450 parts of Water, 540 parts (about 1.5 moles) of a reactantof Formula 1:

C HiOH and 135 parts (about 1.7 moles) of ethylene chlorohydrin areintroduced into a glass reaction vessel equipped with a stirrer and areflux condenser. While being constantly stirred the mass was heated toand maintained in the state of boiling under reflux conditions (105-110C.) continuously for about 16 hours.

At the end of that period the mass is a clear about 30% aqueoussolution, known as Solution 1 and containing approximately 600 partscompound known as Salt 1 and whose formula is:

In this specific example the pH of the solution was 6.3 to 6.7 andfurther heating did not cause the pH to go below 6.3.

EXAMPLE 2 Use same equipment and method described in Example 1. Thereactants are 430 parts (about 1 mole) of a reactant of Formula 2:

4 and parts about (1.1 moles) of ethylene chlorohydrin; and the amountof water is 550 parts. At the end of the 16 hour period of refluxingthere is obtained a clear about 50% aqueous solution known as Solution 2and containing approximately 480 parts of a quaternary ammonium saltknown as Salt 2 and of the formula:

CzHiOH C H -C ON H-C zH4-N CzH4O H C1 C2H40H EXAMPLE 3 Use same methodand apparatus described in Example 1. The reactants are 415 parts (about1 mole) of reactant of Formula 3:

C2H4OH C17H33C 0 0-0 2H4N C2H40H and 150 (about 1.2 moles) of ethylenebromhydrin; and the amount of water is 4500 parts. At the end of the 16hour refluxing period there is obtained a clear about 10% aqueoussolution known as Solution 3 and containing approximately 500 parts ofquaternary ammonium salt known as Salt 3 and of the formula:

EXAMPLES 4-9 Use same method and apparatus as described in Example l,but use 3000 grams of water and as reactants 90 grams (about 1.1 grammoles) of ethylene chlorhydrin and instead of the 515 parts of thereactant of Formula 1 use 1 gram mole of respective reactants which arethe same as reactants of Formula 1 except that for the radical C18H37Substitute a rz 12 25 CIBHHE 18 33 21 43 respectively to obtain fourseparate clear solutions known as Solutions 4-9 respectively andcontaining respective compounds which are the same as Salt 1 except thatsaid radicals are respectively substituted for the C H radical thereof.

EXAMPLES 10-12 Use same method and apparatus as described in Example 2,but use 3000 grams of water and as reactants 90 grams of ethylenechlorhydrin and instead of the 430 parts of the reactant of Formula 2use 1 gram mole of a reactant of that formula except that C17H35 radicalis Substituted C9H19, C11H23, C17H31 respectively to obtain threeseparate clear solutions known as respective Solutions 10-12 andcontaining respective compounds which are the same as Salt 2, exceptthat said radicals are respectively substituted for the C H thereof.

EXAMPLES 13-16 Use same method and apparatus as described in Example 3,but use 3000 grams of water and as reactants grams (about 1.1 grammoles) of ethylene bromhydrin and instead of the reactant of Formula 3use 1 gram mole of reactants of that formula except that the C17H33radical is substituted by cglH g, C17H31, CHI-I23 and C H respectivelyto obtain four separate clear solutions known as Solutions 13-16respectively and containing salts known as Salts 13-16 respectively ofthe same formula as the Salt 3 except that the said radicals arerespectively substituted for the C -H therein.

EXAMPLE 17 Use same method and apparatus of and components in amountsgiven in Example 2, except that for the reactant of Formula 2, use likeamount of a compound which differs therefrom only in the substitution ofCH for the H of the CONH group to obtain a clear solution known asSolution 17 which is of the same formula as Salt 2 except that 0H issubstituted for the H of the CONH group thereof.

EXAMPLE 18ON Use same method and apparatus described in Examples 1-l7,use 3000 grams of water, 100 grams of ethylene chlorhydrin and insteadof the reactants of Formulas l-17 substitute 1 mole of reactants of thesame as Formulas l-l7 except that either one or all of the C l-I groupstherein are substituted by (CH or (CH or one C H group is substituted byone of said groups and another by the other of said groups to obtainmany clear solutions known as Solutions l8-on containing respectivesalts which differ from salts 1-17 by said substitutions in these otherreactants.

Also the same number of moles of ethylene chlorhydrin are substitutedfor the ethylene bromhydrin in all of the foregoing examples where thelatter is used to obtain additional aqueous solutions of the salts whichnow have Br substituted for C1. For example, a salt the same as Salt 3is produced and differs therefrom in the substitution of Cl for the Br.Also the same number of moles of ethylene bromhydrin are substituted forthe ethylene chlorhydrin in all of the examples where the latter is usedto obtain additional aqueous solutions of the salts which now have Clsubstituted for Br. For example, a salt the same as Salt 1 is producedand differs therefrom by the substitution of Br for C1 thereof.

PREFERRED EMBODIMENTS OF THE INVENTION The following examples are givenby way of illustration and not limitation, with all parts being byweight unless otherwise specified.

EXAMPLE 1P Into a glass vessel were charged 40 parts by weight of a 30%aqueous solution of a compound:

while said solution was being constantly stirred there were slowly addedthereto 3 /3 parts by weight of Solution 1 (30% concentration of Salt 1)of Example l. The addi tion was made at room temperature (about 70 F.)and stirring was continued for a period of about ten minutes after thelast increment of Solution 1 was added. At the end of that period theresultant mass contained the reaction product of Salt 1 and IIa in about30% concentration. The resultant mass was visually examined by the nakedeye and found to be crystal clear and is known as Product IF. A sampleof that mass after being allowed to stand over night was so examined andfound to be cloudy.

EXAMPLE 2P The same procedure, components and amounts thereof as setforth in Example 1P were employed except that in this instance thequantity of said Solution 1 was 6 /3 parts instead of the 3 /3 parts byweight. Like before at the end of the ten minute period, the resultantmass contained the Salt 1-IIa reaction product and was visually examinedby the naked eye and found to be crystal clear and was cloudy afterstanding over night and is known as Product 2P.

EXAMPLE 3P The same procedure, components and amounts thereof as setforth in Example 1P were employed except that in this instance thequantity of said Solution 1 was 10 parts instead of the 3% parts byweight. Like before at the end of the ten minute period, the resultantmass contained the Salt l-IIa reaction product and was visually examinedby the naked eye and found to be crystal clear and was cloudy afterstanding over night and is known as Product 3?.

EXAMPLES 4P-33P Use the same procedure and components and amountsthereof as set forth in respective Examples 1P, 2P and SP except thatinstead of using 40 parts of the aqueous solution of IIa, use 40 partsof 30% aqueous solutions respectively of:

IIb

(coconut represents a mixture of the hydrocarbon radicals in the mixedfatty acids of coconut fatty acid).

to provide 30 crystal clear solutions, known as Products 4P-33Prespectively.

All of the Products lP-33P are crystal clear when first made and all ofthem with the exception of Products 1P- 3P remained crystal clearovernight.

EXAMPLE 34P The same procedure and components and amounts thereof as setforth in Examples 1P-3P were used except that instead of using 40 partsof the aqueous solution of I la, there was substituted therefor 20 partsof the aqueous solution of 11a together with 20 parts of a 30% aqueoussolution of 11b. The resulting mass, known as Product 34P, was crystalclear when first made and so remained overnight.

EXAMPLE 35F Into a glass vessel were charged parts of water. Then therewere added thereto 4 parts of Solution 2 of Example 2, approximately 50%concentration of Salt 2. While the liquid in said vessel was beingcontinuously stirred at room temperature there were slowly added thereto100 parts of 30% aqueous solution of 11a. After the last increment of11a solution was added, stirring was continued for an additional periodof about 10 minutes. At the end of that period, the resulting mass,known as Product 35P, containing water soluble reaction product of thecationic and anionic employed was crystal clear as viewed by the nakedeye and so remained overnight.

7 EXAMPLE 36P Employ same procedure, components and amounts thereof asset forth in Example 35F, except that now parts instead of 4 parts ofSolution 2 were used. At the end of the 10 minute period, the resultingmass, known as Product 3-6P, containing water soluble reaction productof the cationic and anionic employed was crystal clear as viewed by thenaked eye and so remained overnight.

EXAMPLE 37P Employ the same procedure, components and amounts thereof asset forth in Example 35F, execept that 14 parts instead of 4 parts ofthe Solution 2 Was used. At the end of the 10 minute period, theresulting mass, known as Product 37F, containing water soluble reactionproduct of the cationic and anionic employed was crystal clear as viewedby the naked eye and so remained overnight. I

EXAMPLES 38P-48P Employ the same procedure, components and amountsthereof as set forth in the respective three Examples 35P-37P, exceptthat instead of using the 5100 parts of the 30% aqueous solution of 11a,use 100 parts of eleven separate 30% aqueous solutions respectively ofIIb-IIl to provide crystal clear solutions, known as Products 38P- 48Prespectively.

EXAMPLE 49P Into a glass vessel were charged 10 parts of Solution 3(about 10% concentration of Salt 3) of Example 3. While beingcontinuously stirred at room temperature, about 70 F, there were slowlyadded thereto 50 parts of a 30% aqueous solution of 11a. After the lastincrement of 11a had been added, stirring was continued for a period ofabout 10 minutes. At the end of that period, the resultant mass, knownas Product 49F was visually examined by the naked eye and found to becrystal clear. Product 49F contained the reaction product of thecationic and anionic employed.

EXAMPLE SOP Employ the same procedure, components and amounts thereof asset forth in Example 49P, except that parts instead of 10 parts ofSolution 3 were used. The resultant mass, known as Product SOP waslikewise examined and found to be crystal clear.

EXAMPLE 5 1 P Employ the same procedure, components and amounts thereofas set forth in Example 49P, except that 40 parts instead of 10 parts ofSolution 2 were used. The resultant mass, known as Product 51P waslikewise examined and found to be crystal clear.

EXAMPLES 52P-82P Employ the same procedure, components and amountsthereof as set forth in the three respective Examples 49P- 51P, insteadof using 50 parts of solution of 11a, use 50 parts of eleven separate30% aqueous solutions of IIb-Ill respectively, whereby there wereproduced 33 more resultant masses, known as Products 52P-82Prespectively.

EXAMPLES 83P-ON Employ the same procedure, components and amountsthereof as set forth in Examples 1P-83P but instead of using Solutions1, 2 and 3, employ respective solutions of corresponding concentrationsof respective salts the same as Salt 1, except that for the C H of Salt1 substitute respective radicals C H *C H and C H respective salts thesame as Salt 2 except that for the C H of Salt 2 substitute respectiveradicals C H C I- C I-I and coconut, respective salts the same as Salt 3except that for the C H thereof substitute respective radicals, CgH C HC H and coconut and/ or instead of using IIa-IIl substitute respectiveanionics: the same as Ila except that the C H thereof substituterespective radicals C H C H and coconut, the same as IIb except that forC H substitute respective radicals C H and C H C H the same as IIcexcept that for C I-I substitute respective radicals C H and C H and CI-I37 and/or instead of 3 have 1, 2, 4, 5, 6, 7, 8, 9, =10, l1 and 12 OCH groups, the same as He and Hg except for the C H and C H groupssubstitute respective radicals C H C18H37 and coconut, and/or for the CHthereof substitute H and C H OH respectively, the same as IIh except forcoconut substitute respective radicals C H C17H33, C H the same as IIi,except for C H substitute 'C H the same as IIj, except substitute C Hfor C H and/ or instead of 4 have 1, 2, 3, 5, 6, 7, 8, 9, 10, 11 and 12O-C H groups, the same as IIk, except for C I-I substitute respectiveradicals C H C H C H and coconut, the same as In substitute for 'C3H17rescpctive radical CQHIQ, C11H23, C17'H33 and COCO- nut. and/ orsubstitute I for CH \All of these hundreds of different products whichmay be produced according to this invention contain the reactionproducts of the cationics and anions employed and upon being producedare crystal clear when visually observed by the naked eye. ISuchproducts are solutions of such reaction products which I believe to bein the nature of complexes. All of such products except those producedby the reaction of cationics of Formula I where n is zero with the alkylsulfates will remain clear upon standing for the conventional periodemployed in determining the shelf life of aqueous soluble shampoocomponent in water.

It is to be understood that wherever M is defined in the presentdescription and claims as sodium that this is not by way of limitationfor the reason that potassium, hydrogen, ammonium or other monovalentcation may be substituted therefor.

Since certain changes in carrying out the above processes andcertainmodifications in the compositions which embody the invention maybe made Without departing from its scope, it is intended that all mattercontained in the above description shall be interpreted as illustrativeand not in a limiting sense.

It is also to be understood that the following claims are intended tocover all the generic and specific features of the invention hereindescribed and all statements of the scope of the invention which as amatter of language might be said to fall therebetween, and that they areintended to be inclusive in scope and not exclusive in that, if desired,other materials may be added to my novel composition of matter hereinclaimed without departing from the spirit of the invention. Particularlyit is to be understood that in'said claims ingredients or componentsrecited in the singular are intended to include mixtures of saidingredients wherever the sense permits.

I claim:

1. A water-soluble organic reaction product of a compound of:

R -OH 3)n NR2 OII Y Cannon and a compound of:

E-A --ZM wherein:

R is a hydrocarbon radical of 8-24 carbon atoms and is alkyl orolefinic;

Each R R and R is an alkylene group of 2-4 carbon atoms;

R is hydrogen or alkyl or 1-4 carbon atoms;

E is a hydrocarbon radical of 6-18 carbon atoms and is alkyl or olefinicor alkyl-aryl, with the aryl portion being mononuclear and the alkylportion being 6-12 carbon atoms;

Z is S 0-80 or CO0;

when m is zero and Z is S0 E is alkyl or alkyl-aryl;

when M is zero and Z is 0-80 E is alkyl or olefinic;

when m is 1 and Z is COO, E is alkyl, olefinic or alkylaryl and A isCN-R6 it.

when m is 1 and Z is OSO E is alkyl, olefinic or alkyl-aryl and A is(O-R or and when m is 1 and Z is S0 E is alkyl, olefinic, or

alkylaryl and A is R is hydrogen or methyl; when R is methyl, R is CHwhen R is hydrogen, R is CH -CH or 511. R is hydrogen, an alkyl radicalof 1-4 carbon atoms or an alkylol radical of 2-4 carbon atoms; M ishydrogen, sodium or potassium or obvious equivalent such ammonium orother monovalent cation; Y is bromine or chlorine; nis zero or 1; m iszero or 1; x is 1-12. 2. A water soluble organic reaction productaccording to claim 1;

n is zero; R1, and R2 are C2H4; R is C18H37; Y is chlorine. 3. A Watersoluble organic reaction product according to claim 1; n is 1;

X is 0-1? H and R R and R are C H R is 17 35;

Y is chlorine. 4. A water soluble organic reaction product according toclaim 2;

m is zero. 5. A water soluble organic product according to claim m is 1.6. A water soluble organic reaction product according to claim 1; I is 0X5H37NC2H4O H 1 C3H4OH and II is C12H25OSO3N3.

7. A water soluble orgarii? reaction product according to claim 1; I is1a 37- C H4OH Cl CzHiOH and II is 8. A water soluble organic reactionproduct according to claim. 1; I is C2H4OH C H 7-N-CzH4OH 9. A watersoluble organic reaction product according 10. A water soluble organicreaction product according to claim 1; I is 11. A water soluble organicreaction product according to claim 1; I is 12 25( 2 4)4 3 12. Themethod comprising reacting in water a cationic compound of Formula I andan anionic compound of Formulas II defined in claim 1.

13. The method according to claim 12; the ratio by weight of thecationic compound to the anionic compound is in the range of about 1-20to 1-1.

14. The method according to claim 12; the ratio by weight of thecationic compound to the anionic compound is in the range of about 1-15to 1-4, and the ratio by weight of the water to the combined weights ofthe anionic and cationic compounds is in the range of about 30-70 toabout .2 to 99.8.

References Cited UNITED STATES PATENTS 3,562,170 2/1971' Zorayan et a1260-401 2,993,918 7/1961 Mannheimer et a1. 260-401 ELBERT L. ROBERTS,Primary Examiner US. Cl. X.R. 252-152; 424-70 UNITED STATES PATENTOFFIQE CE'HMCATE Patent No. 3 661 9H5 Dated Nay 9 1972 Inventor) HansF3. iannheimer It is certified that error appears in theabove-identified patent and that said Letters Patent are herebycorrected as shown below:

In each of Lines M3 and M of Column 2 "n" is deleted and "m" substitutedtherefor.

"I" is placed in the middle of Line 68 :of Column 8.

Column 9 Line 6 "or" 2nd occurrence should read of Column 9 Line 13 "M"-is deleted and "m" substituted therefor. In the last line Claim lH",2-99,8 is deleted and "99.8.2" substituted therefor.

Signed and sealed this 20th day of November 1973.

(SEAT...)

Attest E A I MJ ETCH ER R. RENE D TEG'I'MEYER 4 Attesting Officer ActingCommissioner of Patents FORM 5 (10'69) I USCOMM-DC 60376-P69 9 U,S,GOVERNMENT PRINTING OFFCEI I969 O3$5V33-4

